current research and development in the field of ... · polymers laboratory of...

Bulgarian Academy of ScienceInstitute of Polymers

CURRENT RESEARCH AND DEVELOPMENT IN THE FIELD OF

BIODEGRADABLE POLYMER MATERIALS IN THE INSTITUTE OF

POLYMERS - BAS

M. Ignatova and N. Koseva

3rd International PLASTICE ConferenceOctober 1-2nd 2013, Warsaw, Poland

e-mails: [email protected]@polymer.bas.bg

Bulgarian Academy of SciencesBulgarian Academy of Sciences

Institute of PolymersInstitute of Polymers

Tel:/Fax: +359(2)870-03-09http://www.polymer.bas.bg

Acad. G. Bonchev St., bl. 103A1113 Sofia, Bulgaria

Institute of Polymers – Structural organization

IP-BAS is a scientific entity with 60 employees. Research staff – 49Administration – 6 Other - 5

INSTITUTE OF POLYMERS

Laboratory ofAmphiphilic

and IonogenicPolymers

Laboratory ofBioactivePolymers

Laboratory ofStructure andProperties of

Polymers

Laboratory ofPhosphorus-Containing

Monomers andPolymers

Laboratory ofConjugatedPolymers

Laboratory ofPolymerization

Processes

The Institute of Polymers is an autonomous research unit that belongs to theNanosciences, New Materials and Technologies Division of the Bulgarian Academy of Sciences

Institute of Polymers – Structural organization

Research staff Scientists- 4 full professors, 12 associate professors; 22 assistant professors Research supporting staff - 11 university or high technical school graduates. 12 PhD students are trained at IP-BAS.

The young researcher staff has ever been considered one of the most important advantages of the Institute of Polymers and much efforts have been put into encouraging the young generation to built their career at home

Institute of Polymers – Prospects for Development

(i) Synthesis, modification and characterization of polymers

(ii) Development of new polymer materials with tailored properties

Materials for agriculture and

food preservation

IP-BAS excellence in design and synthesis of polymers

with valuable properties :biodegradable, biocompatible,

stimuli sensitive, self-organizing, electroactive, etc.

Materials for pharmacy, medicine and biotechnology

Materials for alternative

energy production

Materials for environmental

monitoring, preservation and

recovering

Mission - to do advanced research and education on polymers and polymer materials and to transform the generated knowledge into innovative materials and processes in response to the needs of industry and society.

Institute of Polymers – Mission Statement and Research Priorities

A considerable part of the research includes investigations on biodegradable polymer materials – design and application.

Biobased and (bio)degradable polymers

Polysaccharides

Proteins

Extracted from biomass

By polymerization of monomers derived from

renewable sources

Produced by bacterial

fermentation

Poly(lactic acid)and copolymers

Poly(hydroxyalkanoates)

Microbial cellulose

Plantorigin

Marineorigin

Novel materials for biomedical, agricultural and food applications

today

10 days later

http://www.biocorpusa.com/html/pla_clear_cup.html

120nm

+

POE

POE

+

beads

micro- and nanofibers

capillaryextrusion

coprecipitation

hydrogels

electrospinning

nanoparticles

Institute of Polymers – Research Priorities

Laboratory of Bioactive Polymers


Laboratory of Bioactive PolymersChitosan, N-carboxyethylchitosan(polyelectrolyte complexes at pH 1-14)

CECh/PDMAEMA

CECh/PDMAEMAQ100

CECh/PDMAEMA, blood

OOH

NH2HOO

OH

NH2

OO

NHCOCH3

OHO

OO

HO

HOO

OH

OHO

NH2COCH3OHO

OH

O

H2NCH2CH2

COO-

O O

OH

HONH3

OHO

OH

O

HNCH2CH2

COOHCH2CH2

-OOC

+

+

+

+

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Chit/PAA

Chit/PAMPS

Chit/P(AMPS-co-AA)

CECh/PAMPS

CECh/PAA

CECh/PEI

CECh/PDMAEMA

CECh/PDMAEMAQ50

CECh/PDMAEMAQ100

pHE. Yancheva, D. Paneva, V. Maximova, L. Mespouille,Ph. Dubois, N. Manolova, I. Rashkov, Biomacromolecules 8: 976-984 (2007)E. Yancheva, D. Paneva, D. Danchev, L. Mespouille,Ph. Dubois, N. Manolova, I. Rashkov, Macromol. Biosci. 7: 940–954 (2007)

COONa

COO-

OOH

O

NHO OHO

OH

HO HO

OH

HOOO

O

OHO

H2N+

+NH

-OOC

+NH3

COCH3

I-

114n

C OOCH2

CH2

N+

H3CH3C

H3C

C CH2

CH3Br

CH3

CH3O

C O CH2CH2O CH3114m

CH CH2

CH3

CH3

BrOC O CH2CH2O CH3

SO3-, Na+

CH2

CH3H3C CNH

OC

H3C OO

O

O CH3

CH3

CH3

BrC OO

NH3C CH3

114 n

STEALTH NANOPARTICLES FROM N-CARBOXYETHYLCHITOSAN



R. Mincheva, D. Paneva, L. Mespouille, N. Manolova, I. Rashkov, Ph. Dubois, J. Polymer Sci. Part A.,Polym. Chem., 47(4): 1108-1119 (2009)R. Mincheva, F. Bougard, D. Paneva, M. Vachaudez, Ch. A. Fustin, J.-F. Gohy, N. Manolova, I. RashkovPh. Dubois, J. Polym. Sci, Part A, 47(8): 2105-2117 (2009)R. Mincheva, F. Bougard, D. Paneva, M. Vachaudez, N. Manolova, Ph. Dubois, I. Rashkov, Biomacromolecules, 10: 838-844 (2009)

Preparation of PHB/montmorillonite (MMT) nanocomposites by solution intercalation method.

Application of organomodified clay “Cloisite®30B” for preparation of the nanocomposites - weight ratio polymer/clay in the range form 0 wt.% up to 10 wt.%

Characterization of the nanocomposites by DSC, XRD, IR, optical microscope and mechanical testing

Till now the XRD results obtained show that, at filler loadings higher than 3 wt. %, intercalation of the clay with polymer matrix is observed. At lower clay concentrations, exfoliation dominates.

PHB is fully renewable biodegradable and biocompatible thermoplastic polymerproduced by microorganisms.

Biodegradable nanocomposites based on polyhydroxybutyrate (PHB)

Scheme of types of obtained nanocomposite structures


Laboratory of Conjugated Polymers



antibacterial non-woven textile haemostatic non-woven textilewound healing devices

scaffolds for cell andtissue engineering

fullerene-containing nanofibers

> 200 cells/100 μm2 ~ 5 cells/100 μm2

× 1500× 200hhνν

33OO2211OO22

Destruction Destruction of tumor cellsof tumor cells

NANOFIBROUS MATERIALS FROM BIOCOMPATIBLE AND BIODEGRADABLE POLYMERS WITH TAILORED

BIOLOGICAL PROPERTIES ON CONTACT WITH CELLS

N

Cl

Cl H

O

O- Na+ N

CH3

CH3 O

H

HN

C2H5

C2H5Cl+

-

SEM micrograph ofdrug-loaded PLA/PEG bundle

PEG

Poly(L-lactide)

O C H

C H3

CO

n

CH2 CH2 Om

Multi-needleelectrode

Cl+

-CH2 N CH3

R

CH3

Lidocaine hydrochloridelocal anesthetic

Diclofenac sodiumanti-inflammatory agent

Multi-needle electrode

-

collector

???? ??????????????

jet?????

needle

-

Al ????+

+

-

syringe containingpolymer solution

syringe needle

Taylor cone

screen-

Al foil+

+

Benzalkonium chlorideantibacterial

Drug-Loaded Electrospun Polylactide Bundles



А. Toncheva, M. Spasova, D. Paneva, N. Manolova, I. Rashkov ,Journal of Bioactive and Compatible Polymers 26:161-172 (2011)

Tuning of the Surface Biological Behavior of Poly(L-Lactide)-Based Electrospun Materials by Polyelectrolyte Complex Formation



Yancheva E., Paneva D., Manolova N., Mincheva R., Danchev D., Dubois Ph., Rashkov I., Biomacromolecules 11: 521-532 (2010)

Non-traumatic wound dressing

A laboratory know-how for electrospinning directly onto the injured tissue of patient's hand

[email protected]



www.bioactivepolymers-bas.org



Apoptosis in HeLa human cervical cancer cells

coPLA

QCh/coPLA/DOX

Antitumor activity of electrospun implants against

Graffi myeloid tumor

Antitumor activity of electrospun nanofibrous materials containing quaternized chitosan, poly(L-lactide-co-D,L-lactide) and doxorubicin

Ignatova M., Manolova N., Toshkova R., Rashkov I., Gardeva E., Yossifova L., Alexandrov M., Biomacromolecules 11: 1633-1645 (2010).Toshkova R., Manolova N., Gardeva E., Ignatova M., Yossifova L., Rashkov I., Alexandrov M., Int. J. Pharm. 400: 221-233 (2010).

Lab-scale technology forembedding of biopesticide (T. viride) in a fibrous membrane from biodegradable polymer chitosan

Stimulates the plant protectionImpedes the development of plant pathogensProvides favorable conditions for plant growth

Environmentally friendlyplant protection systemsbased on chitosan



a protectivefibrous membrane

M. Spasova, N. Manolova, M. Naydenov, J. Kuzmanova, I. Rashkov, Journal of Bioactive and Compatible Polymers 26:48–55 (2011).



Control“Tricho-kit”

Cucumbers

Fusaruim

Fusaruim

“Tricho-kit” against Fusaruim

www.bioactivepolymers-bas.org


Laboratory of Phosphorus-containing Monomers and Polymers

OP

O

O

H

Addition reactions to С=О, С=С and C=N

Poly(HPoly(H--phosphonate)phosphonate)

Polyphosphonate

Oxidative chlorinationAtherton-Todd reaction

Polyphosphates

OP

O

O

CR'R''YO

P

O

O

NR'R''

Polyphosphoramidate

OP

O

O

OR'

NHR'R″

HOR’

NH2R'.HCl

OP

O

O

ONH3R'-+ Polysalt

Biocompatible/biodegradable phosphorus-containig polymers

Radioprotectors (Cysteamine, WR2721)Anticancer agents (bendamustine HCl)Antiviral agents (azidothymidine, AZT)

Drug-Polymer Conjugates

Chemical degradation of polymers by esters of H-phosphonic and phosphoric acids

C NH CH2)( 4 O C

O

CH2)( C

O

O )(24 CH2 O nCH2 NH C

O

O

O

Chemical Degradation of Polyurethanes

Chemical Degradation of Polycarbonate

Chemical Degradation of Polyamide

The chemical transformation of polymer waste into new phosphor‐containing oligomers which can be used for preparation of polymers with new properties. The main aim of the recycling of polymer waste materials and used polymers is conservation of the natural resources and reduction of environmental stress. The degradation products can be used successfully for the preparation of rigid polyurethanes with improved exploitation characteristics (high density and good mechanical properties).


Laboratory of Phosphorus-containing Monomers and Polymers

Scientific Equipment

• Differential scanning calorimeter DSC-8500 Perkin Elmer;• TGA-4000 Perkin Elmer;• Analytical ultracentrifuge ProteomeLab XL-I Beckman Coulter• Universal modular rheometer RheoStress 600, Thermo Haake;

• LDC-SJP-35 single screw extrusion pelletizer line;• HZ-1005B dynamometer;• HZ-1072A cantilever beam impact testing machine;• IR spectrometers: Vector 22 Bruker and IRAffinity-1 Shimadzu FTIR; • UV-VIS spectrometer DU 800 (Beckman Coulter);• Electrospinning equipment

The Institute is a co-owner of a Bruker Avance II+ 600 NMR spectrometer.

• GPC Waters equipment for determination of molecular weight and molecular weight distribution of polymers;• DAWN DSP Wyatt for determining the absolute molecular mass and particles size via light scattering;• AVS-310 Schott Gerate automatic viscometer;• Stanton Redcroft apparatus for determining the limiting oxygen index;• Optical microscopes Zetoplan NU-2, Reicher and DMLP Leica;• Microwave reactor RotoSYNTH (Milestone s.r.l.);

Institute of Polymers – Tradition and Competence in Polymer Research and Innovations

PROJECTSPROJECTS

FUNDED BY ECFP-7 Projects• POLINNOVA - Strengthening the Research Capacity and Innovation Potential of the Institute of Polymers at the Bulgarian Academy of Sciences for Further Integration into the ERA, Coordination and Support Action, No. 316086.• PASPORT Plan of Action - a Strategic Portal to Research Excellence (CAPACITIES; REGPOT-2; 2008-9)•SEE-ERA-NET Pilot Joint Call - Immobilized Yeast Cells in Hydrogel Carriers for Bioproduction of Alcohols (SEE-ERA-NET; 2008)FP-6 Projects• AUTOBRANE: Automotive High Temperature Fuel Cell Membranes, No. 020074 (SЕS6)• CARISMA: Coordinated Action of Research on Intermediate and High Temperature Specialized Membrane Electrode Assemblies, No. 039041

FUNDED BY STRUCTURAL FUNDS:“Human Resources Development” Programme: Support for the Development and Career of PhD Students, Post-doc Fellows and

Young Scientists in the Field of Polymer Chemistry, Physics and Engineering OP "Development of the Competitiveness of the Bulgarian Economy“: Support to the application research at the IP-BAS for development polymer and composite materials.

FUNDED BY THE NATIONAL SCIENCE FUND Center of Excellence: NATIONAL CENTER FOR ADVANCED MATERIALS - UNION Module 2: New materials for medicine and pharmacy• Novel Hybrid Nanostructured Materials for Local Cancer Treatment• New Polymeric Delivery Systems of Antitumor Platinum Coordination Compounds• Polymeric Nanotraps for Immobilization and Delivery of Biomacromolecules• Self-assembly of Conducting Nanofibers into Yarns During Electrospinning of Polyelectrolyte Solutions• Novel Nanocomposites Polyolefin/Lamellar Silicate with Improved Thermal Stability and Enhanced Mechanical Properties• New Antibacterial and Hemostatic Nanofibrous Wound Dressings• Study of the Interaction Chitosan (Solutions, Microgels or Nanostructured Spheres) – Beneficial/Pathogenic

Microorganisms – Agricultural Crops• Novel Functional Nanostructured Materials for Electrochemical Detection of Pesticides in Foods• Appliances Development and Technologies for Electrospinning of Biopolymers for Preparation of Nanofiber Materials

(NANOBIOMAT)•Hollow Polymeric Nanospheres and Nanocylinders•PEM Hydrogen

Institute of Polymers – International Collaboration

IP-BAS has been fostering high-level bilateral cooperation with academic institutions from Europe and the rest of the world - Germany, France, Belgium, Switzerland, the Czech Republic, Poland, Spain, Italy, UK, Greece, Turkey, Romania, Russia, Ukraine, Belarus, Japan, USA.

IP-BAS is a co-founder of the Central and East European Polymer Network which is an informal association of polymer institutes and polymer groups affiliated to national academies of sciences in eight Central- and East- European countries.

OTHER RESEARCH GROUPS IN BULGARIA WORKING IN THE FIELD OF BIODEGRADABLE POLYMER MATERIALS

Faculty of Chemical Technology,Department of Polymer Engineering,Head: Prof. Nikolai Dishovsky, DSc,

E-mail: [email protected]

Faculty of Chemical and System Engineering, Department of

Biotechnology, Head: Prof. Lyubov Yotova, PhD,


UNIVERSITY OF SOFIA"ST. KLIMENT

OHRIDSKI"

Faculty of Chemistry and Pharmacy, Department of Applied Organic Chemistry,

Laboratory of Polymers, Head: Prof. Michail Evstatiev, DSc,


UNIVERSITY OF CHEMICAL TECHNOLOGY AND

METALLURGY, SOFIA

Branch organization Bulgarian Association Polymers (BAP)

http://www.bap-bg.org//

It represents 37 Bulgarian companies processing and marketing polymers and plastics.

BAP is active affiliate of the Bulgarian Institute for Standardization and a member of the European Plastics Converters Association (EUPC).

BAP actively monitors the alteration in the Bulgarian and European legislation concerning the plastics industry and business preserving interests, and also cooperates with the Bulgarian authorities in the country legislation making process.

BAP implements a set of communication activities used to promotethe image of the company and their products, and to support the introduction of new products to the market.

The memorandum, signed between BAP and the Institute of Polymers-BAS, by the project POLINNOVA, mapped the joint activities and the commitment of BAP to mediate for establishment of firm contacts between the Institute of Polymers and representatives of the polymer industry.

COMPANY EXTRAPACK Ltd.

• Extrapack Ltd. is the first company in Bulgaria with 100% automatized production of paper bags for shopping, and the only manufacturer of bags ECOFLEX®, produced from 100% compostable, biodegradable polymer. Extrapack Ltd. produces different plastic bags and packages made from DEGRALEN®.• For recycling purposes Extrapack Ltd. has built a plant with total capacity of over 500 kg/per hour.

EXTRAPACK – factoryVeliko Tarnovo 5000, BulgariaZapadna Promishlena ZonaTel. (+359-62) 611-515, 611-511Fax: (+359-62) 611-556

For contacts: EXTRAPACK Sofia branchSofia 1712, Mladost 3, ul. eng. Georgi Belov 20aTel. ( +359-2) 975 30 68; 975 35 47; 8177 910Fax ( +359-2 ) 975 10 80, [email protected]

• established in 1995 by five young enterprisers, whose efforts have been directed towards creating a company that is a leader in the polyethylene packaging production. • In the spring of 2000 Extrapack made a "green field investment", launching a big modern plant, located in the West industry area of Veliko Turnovo town.• At present it has over 400 employees with annual turnover of more than 18 millions of Euro.

Products of the company: Non-biodegradable polymer bags, paper bags and biodegradable polymer bags

luxury bags t-shirt bags photoprinted bags patch handle bags bags for gift flat bags garbage bags plastic envelopes

Packages for industry

foil and film small and large bags impulse sealersPlastic and paper cups, boxes, bottles, plates, knives, spoons and forksOther standard products (necessary and practical products for home, office or fast food: raincoat, table-

cloth, bags for sandwiches, foil for painting).

Bulgarian Academy of Science Institute of Polymers

All researchers of the Institute of Polymers are members of the Bulgarian Polymer Society –

full member of the European Polymer Federation

current research and development in the field of ... · polymers laboratory of...

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